U.S. patent number 6,893,564 [Application Number 10/157,182] was granted by the patent office on 2005-05-17 for shaped bodies containing metal-organic frameworks.
This patent grant is currently assigned to BASF Aktiengesellschaft, The Regents of the University of Michigan. Invention is credited to Mohamed Eddaoudi, Michael Hesse, Lisa Lobree, Ulrich Mueller, Omar Yaghi.
United States Patent |
6,893,564 |
Mueller , et al. |
May 17, 2005 |
Shaped bodies containing metal-organic frameworks
Abstract
The present invention relates to a novel class of shaped bodies
containing metal-organic frameworks. Said metal-organic frameworks
comprise at least one metal ion and at least one at least bidentate
organic compound and contain at least one type of micro- and
mesopores or micro- or mesopores. Said shaped bodies comprise at
least one metal-organic framework material and may optionally
contain further substances, in particular at least one supporting
material.
Inventors: |
Mueller; Ulrich (Neustadt,
DE), Lobree; Lisa (Mannheim, DE), Hesse;
Michael (Worms, DE), Yaghi; Omar (Ann Arbor,
MI), Eddaoudi; Mohamed (Ann Arbor, MI) |
Assignee: |
BASF Aktiengesellschaft
(Ludwigshafen, DE)
The Regents of the University of Michigan (Ann Arbor,
MI)
|
Family
ID: |
29582409 |
Appl.
No.: |
10/157,182 |
Filed: |
May 30, 2002 |
Current U.S.
Class: |
210/502.1;
210/503; 502/153; 554/225; 540/465; 502/154; 502/152; 210/510.1;
502/151; 264/239 |
Current CPC
Class: |
B01J
20/28004 (20130101); B01J 20/28042 (20130101); B01J
20/28014 (20130101); B01J 39/16 (20130101); B01J
20/28011 (20130101); B01J 20/226 (20130101); B01J
20/3042 (20130101); B82Y 30/00 (20130101); B01J
31/1691 (20130101); B01J 20/281 (20130101); B01J
20/3007 (20130101); B01J 20/282 (20130101); B01J
20/2803 (20130101); B01J 20/28045 (20130101); C02F
1/42 (20130101); C02F 1/28 (20130101); B01J
2220/82 (20130101); B01J 2220/54 (20130101); B01D
2257/93 (20130101) |
Current International
Class: |
B01J
20/28 (20060101); B01J 20/22 (20060101); B01J
39/16 (20060101); B01J 39/00 (20060101); C02F
1/28 (20060101); C02F 1/42 (20060101); B01D
039/00 (); C07F 009/00 () |
Field of
Search: |
;210/502.1,503,510.1,502
;502/150,151,152,153,154,401 ;540/465 ;554/225 ;264/239 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0 790 253 |
|
Aug 1997 |
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EP |
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99/05151 |
|
Feb 1999 |
|
WO |
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02/070526 |
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Sep 2002 |
|
WO |
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02/088148 |
|
Nov 2002 |
|
WO |
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03/035717 |
|
May 2003 |
|
WO |
|
Other References
Kerpert, et al., "A Porous Chiral Framework of Coordinated
1,3,5-Benzenetricarboxylate: Quadruple Interpenetration of the
(10,3)-A Network," Chemical Communications, Royal Society of
Chemistry, GB, vol. 1, 1998, pp. 31-32. .
Yahgi, et al., "Selective Binding and Removal of Guests in a
Microporous Metal-Organic Framework," Nature, Macmillan Journals
Ltd., London, GB, vol. 378, No. 6558, Dec. 14, 1995, pp. 703-706.
.
Yaghi, et al., "Constructions of Porous Solids from Hydrogen-Bonded
Metal Complexes of 1,3,5-Benezenetricarboxylic Acid," Journal of
the Americal Chemical Society, American Chemical Society,
Washington, DC, US, vol. 118, No. 38, 1996, pp. 9096-9101. .
Derwent Abstracts, DE 100 32 885, Jan. 17, 2002. .
Derwent Abstracts, DE 100 32 884, Jan. 24, 2002. .
Derwent Abstracts, DE 100 15 246, Oct. 4, 2001. .
Derwetn Abstracts, WO 2000/07 965, Feb. 17, 2000. .
M. O. Keeffe, et al., Journal of Solid State Chemistry, 152, pp.
3-20, "Frameworks for Extended Solids: Geometrical Design
Principles", 2000. .
H. Li, et al., Letters to nature, vol. 402, pp. 276-279, "Design
and Synthesis of an Exceptionally Stable and Highly Porous
Metal-Organic Framework", Nov. 18, 1999. .
M. Eddaoudi, et al., Topics in Catalysis, vol. 9, pp. 105-111,
"Design and Synthesis of Metal-Carboxylate Frameworks with
Permanent Microporosity", 1999. .
B. Chen, et al., Science, vol. 291, pp. 1021-1023, "Interwoven
Metal-Organic Framework on a Periodic Minimal Surface with
Extra-Large Pores", Feb. 9, 2001..
|
Primary Examiner: Kim; John
Attorney, Agent or Firm: Oblon, Spivak, McClelland, Maier
& Neustadt, P.C.
Claims
What is claimed is:
1. A shaped body comprising a porous metal-organic framework
material, prepared by molding a composition comprising a porous
metal-organic framework material or contacting at least one
substrate with at least one metal-organic framework material,
wherein said metal-organic framework material comprises at least
one metal ion and at least one at least bidentate organic compound
which is coordinately bonded to said metal ion; wherein the shaped
body extends in at least one direction in space by at least 0.02 mm
and does not extend in any direction in space by more than 50 mm;
and wherein the shaped body has a resistance to pressure (crush
strength) in the range of from 2 N to 100 N.
2. The shaped body according to claim 1, wherein the shaped body is
in the form of a pellet having a diameter in the range from 1.5 mm
to 5 mm and a height in the range from 1 mm to 5 mm.
3. A process for preparing the shaped body according to claim 1,
wherein the shaped body is prepared by at least one step of molding
a composition comprising a porous metal-organic framework
material.
4. The process according to claim 3, wherein said molding is
selected from the group consisting of briquetting by piston
presses, briquetting by roller pressing, binderless briquetting,
briquetting with binders, pelleting, compounding, melting,
extruding, co-extruding, spinning, deposition, foaming, spray
drying, coating, granulating and spray granulating.
5. The process according to claim 3, wherein the composition
further comprises at least one binder, and the binder is selected
from the group consisting of a hydrated alumina or other aluminum
containing binders, mixers of silicon and aluminum compounds,
silicon compounds, clay minerals, alkoxysilanes, amphiphilic
substances and graphite.
6. A process for preparing a shaped body according to claim 1,
comprising contacting at least one substrate with at least one
metal-organic framework material.
7. The process according to claim 6, wherein said contacting is
selected from the group consisting of impregnating said substrate
with a fluid comprising the metal-organic framework material,
soaking said substrate in a fluid comprising the metal-organic
framework material, spraying said substrate the metal-organic
framework material, depositing the metal-organic framework material
from the liquid phase on the substrate, depositing the
metal-organic framework material from the gas phase (vapor
deposition) on the substrate, precipitating the metal-organic
framework material on the substrate, co-precipitating the
metal-organic framework material on the substrate, dipping
substrate in the metal-organic framework material, and coating the
substrate with the metal-organic framework material.
8. The process according to claim 3, wherein the shaped body has at
least one of the following features: (i) the shaped body is in the
form of a monolith, (ii) the shaped body is in the form of a
two-dimensional body, (iii) the metal organic framework material is
part of a wash-coat, (iv) the shaped body has a skeleton-like or a
honeycomb-like topology.
9. The process according to claim 6, wherein the shaped body has at
least one of the following features: (i) the shaped body is in the
form of a monolith, (ii) the shaped body is in the form of a
two-dimensional body, (iii) the metal organic framework material is
part of a wash-coat, (iv) the shaped body has a skeleton-like or a
honeycomb-like topology.
10. A reaction comprising reacting reactants in the presence of the
shaped body of claim 1, wherein said reacting is carried out in a
fixed bed reactor, a packed bed reactor, or said shaped body is
suspended in a slurry.
11. A catalyst comprising the shaped body of claim 1.
12. A catalyst support comprising the shaped body of claim 1.
13. A sorption material comprising the shaped body of claim 1.
14. A fluid storage material comprising the shaped body of claim
1.
15. A dessicant comprising the shaped body of claim 1.
16. An ion exchange material comprising the shaped body of claim
1.
17. A molecular sieve comprising the shaped body of claim 1.
18. A chromatography material comprising the shaped body of claim
1.
19. A selective release material comprising the shaped body of
claim 1.
20. A material for absorbing or adsorbing molecules comprising the
shaped body of claim 1.
21. A molecular recognition material comprising the shaped body of
claim 1.
22. A nanotube comprising the shaped body of claim 1.
23. A nano-reactor comprising the shaped body of claim 1.
Description
The present invention relates to a novel class of shaped bodies
containing metal-organic frameworks. Said metal-organic frameworks
comprise at least one metal ion and at least one at least bidentate
organic compound and at least one type of micro- and mesopores or
micro- or mesopores. Said shaped bodies comprise at least one
metal-organic framework material and may optionally contain further
substances, in particular at least one supporting material.
Materials displaying a large internal surface area, preferably
defined by pores or channels, are of predominant interest for
applications in catalysis, for absorption and/or adsorption
techniques, ion exchanging, chromatography, storage and/or uptake
of substances, among others. The preparation of solid porous
materials according to the present state of the art is described,
for example, in Preparation of Solid Catalysts, Gerhard Ertl,
Helmut Knozinger, Jens Weitkamp (Eds.), Wiley VCH, Weinheim, 1999.
Here, solid porous materials are prepared by precipitation, sol-gel
processes, spray-drying, foaming etc.
In a promising novel and alternative synthesis strategy to create
micro- and/or mesoporous active materials, metal ions and molecular
organic building blocks are used to form so-called metal-organic
frameworks (MOFs). The metal-organic framework materials as such
are described, for example, in U.S. Pat. No. 5,648,508, EP-A-0 709
253, M. O'Keeffe et al., J. Sol. State Chem., 152 (2000) p. 3-20,
H. Li et al., Nature 402 (1999) p. 276 seq., M. Eddaoudi et al.,
Topics in Catalysis 9 (1999) p. 105-111, B. Chen et al., Science
291 (2001) p. 1021-23. Among the advantages of these novel
materials, in particular for applications in catalysis, are the
following: (i) larger pore sizes can be realized than for the
zeolites used presently (ii) the internal surface area is larger
than for porous materials used presently (iii) pore size and/or
channel structure can be tailored over a large range, (iv) the
organic framework components forming the internal surface can be
functionalized easily.
However these novel porous materials as such, based on
metal-organic frame-works, are generally obtained as small
crystallites or powders and--in this form--cannot be put to use in
applications that require shaped bodies.
It is therefore an object of the present invention to provide a
shaped body displaying the characteristic properties of the
materials containing metal-organic frameworks. The term "shaped
body" as used in the present invention thereby refers to shaped
bodies obtained by molding processes and to shaped bodies obtained
by applying the active material onto a (porous) substrate. The term
"shaped body" will be defined further below.
This object is solved by subjecting at least one material
containing a metal-organic framework comprising pores and at least
one metal ion and at least one at least bidentate organic compound,
which is coordinately bound to said metal ion, to a molding step or
to apply said material onto a substrate or to perform a combination
of both operations. Thus, the present invention relates to a
metal-organic framework material comprising pores and at least one
metal ion and at least one at least bidentate organic compound,
which is coordinately bounded to said metal ion characterized in
that it is in the form of a shaped body, a process for
manufacturing the metal-organic framework material that is in the
form of a shaped body as described herein, characterized in that
the shaped body is obtained by at least one step of molding, a
process for manufacturing a metal-organic framework material that
is in the form of a shaped body as described herein, characterized
in that the shaped body is obtained by contacting at least one
metal-organic framework material with at least one substrate, and
the use of said framework materials as described herein, as
catalyst, support for catalysts, for sorption, storage of fluids;
as desiccant, ion exchanger material, molecular sieve (separator),
material for chromatography, material for the selective release
and/or uptaking of molecules, molecular recognition, nanotubes,
nano-reactors.
As has been mentioned above, the metal-organic framework material
is described in, for example, U.S. Pat. No. 5,648,508, EP-A-0 709
253, M. O'Keeffe et al., J. Sol. State Chem., 152 (2000) p. 3-20,
H. Li et al., Nature 402 (1999) p. 276 seq., M. Eddaoudi et al.,
Topics in Catalysis 2 (1999) p. 105-111, B. Chen et al., Science
291 (2001) p. 1021-23. An inexpensive way for the preparation of
said materials is the subject of DE 10111230.0. The content of
these publications, to which reference is made herein, is fully
incorporated in the content of the present application.
The metal-organic framework materials, as used in the present
invention, comprise pores, particularly micro- and/or mesopores.
Micropores are defined as being pores having a diameter of 2 nm or
below and mesopores as being pores having a diameter in the range
of 2 nm to 50 nm, according to the definition given in Pure Applied
Chem. 45, p. 71 seq., particularly on p. 79 (1976). The presence of
the micro- and/or mesopores can be monitored by sorption
measurements which determine the capacity of the metal-organic
framework materials for nitrogen uptake at 77 K according to DIN
66131 and/or DIN 66134.
For example, a type-I-form of the isothermal curve indicates the
presence of micropores [see, for example, paragraph 4 of M.
Eddaoudi et al., Topics in Catalysis 9 (1999)]. In a preferred
embodiment, the specific surface area, as calculated according to
the Langmuir model (DIN 66131, 66134) preferably is above 5 m.sup.2
/g, further preferred above 10 m.sup.2 /g, more preferably above 50
m.sup.2 /g, particularly preferred above 500 m.sup.2 /g and may
increase into the region above 3000 m.sup.2 /g.
As to the metal component within the framework material that is to
be used according to the present invention, particularly to be
mentioned are the metal ions of the main group elements and of the
subgroup elements of the periodic system of the elements, namely of
the groups Ia, Ia, IIIa, IVa to VIIIa and Ib to VIb. Among those
metal components, particular reference is made to Mg, Ca, Sr, Ba,
Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co,
Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge,
Sn, Pb, As, Sb, and Bi, more preferably to Zn, Cu, Ni, Pd, Pt, Ru,
Rh and Co. As to the metal ions of these elements, particular
reference is made to: Mg.sup.2+, Ca.sup.2+, Sr.sup.2+, Ba.sup.2+,
Sc.sup.3+, Y.sup.3+, Ti.sup.4+, Zr.sup.4+, Hf.sup.4+, V.sup.4+,
V.sup.3+, V.sup.2+, Nb.sup.3+, Ta.sup.3+, Cr.sup.3+, Mo.sup.3+,
W.sup.3+, Mn.sup.3+, Mn.sup.2+, Re.sup.3+, Re.sup.2+, Fe.sup.3+,
Fe.sup.2+, Ru.sup.3+, Ru.sup.2+, Os.sup.3+, Os.sup.2+, Co.sup.3+,
Co.sup.2+, Rh.sup.2+, Rh.sup.+, Ir.sup.2+, Ir.sup.+, Ni.sup.2+,
Ni.sup.+, Pd.sup.2+, Pd.sup.+, Pt.sup.2+, Pt.sup.+, Cu.sup.2+,
Cu.sup.+, Ag.sup.+, Au.sup.+, Zn.sup.2+, Cd.sup.2+, Hg.sup.2+,
Al.sup.3+, Ga.sup.3+, In.sup.3+, Tl.sup.3+, Si.sup.4+, Si.sup.2+,
Ge.sup.4+, Ge.sup.2+, Sn.sup.4+, Sn.sup.2+, Pb.sup.4+, Pb.sup.2+,
As.sup.5+, As.sup.3+, As.sup.+, Sb.sup.5+, Sb.sup.3+, Sb.sup.+,
Bi.sup.5+, Bi.sup.3+ and Bi.sup.+.
With regard to the preferred metal ions and further details
regarding the same, particular references is made to: U.S. Pat. No.
5,648,508, particularly to col. 11, lines 10ff, section "The Metal
Ions" which section is incorporated herein by reference.
In addition to the metal salts disclosed in EP-A 0 790 253 and U.S.
Pat. No. 5,648,508, other metallic compounds can be used, such as
sulfates, phosphates and other complex counter-ion metal salts of
the main- and subgroup metals of the periodic system of the
elements. Metal oxides, mixed oxides and mixtures of metal oxides
and/or mixed oxides with or without a defined stoichiometry are
preferred. All of the above mentioned metal compounds can be
soluble or insoluble and they may be used as starting material
either in form of a powder or as a shaped body or as any
combination thereof.
As to the at least bidentate organic compound, which is capable of
coordination with the metal ion, in principle all compounds can be
used which are suitable for this purpose and which fulfill the
above requirements of being at least bidentate. Said organic
compound must have at least two centers, which are capable to
coordinate the metal ions of a metal salt, particularly with the
metals of the aforementioned groups. With regard to the at least
bidentate organic compound, specific mention is to be made of
compounds having i) an alkyl group substructure, having from 1 to
10 carbon atoms, ii) an aryl group substructure, having from 1 to 5
phenyl rings, iii) an alkyl or aryl amine substructure, consisting
of alkyl groups having from 1 to 10 carbon atoms or aryl groups
having from 1 to 5 phenyl rings,
said substructures having bound thereto at least one at least
bidentate functional group "X", which is covalently bound to the
substructure of said compound, and wherein X is selected from the
group consisting of
CO.sub.2 H, CS.sub.2 H, NO.sub.2, SO.sub.3 H, Si(OH).sub.3,
Ge(OH).sub.3, Sn(OH).sub.3, Si(SH).sub.4, Ge(SH).sub.4,
Sn(SH).sub.3, PO.sub.3 H, AsO.sub.3 H, AsO.sub.4 H, P(SH).sub.3,
As(SH).sub.3, CH(RSH).sub.2, C(RSH).sub.3, CH(RNH.sub.2).sub.2,
C(RNH.sub.2).sub.3, CH(ROH).sub.2, C(ROH).sub.3, CH(RCN).sub.2,
C(RCN).sub.3, wherein R is an alkyl group having from 1 to 5 carbon
atoms, or an aryl group consisting of 1 to 2 phenyl rings, and
CH(SH).sub.2, C(SH).sub.3, CH(NH.sub.2).sub.2, C(NH.sub.2).sub.2,
CH(OH).sub.2, C(OH).sub.3, CH(CN).sub.2 and C(CN).sub.3.
Particularly to be mentioned are substituted or unsubstituted,
mono- or polynuclear aromatic di-, tri- and tetracarboxylic acids
and substituted or unsubstituted, at least one hetero atom
comprising aromatic di-, tri- and tetracarboxylic acids, which have
one or more nuclei.
A preferred ligand is 1,3,5-benzene tricarboxylic acid (BCT).
Further preferred ligands are ADC (acetylene dicarboxylate), NDC
(naphtalene dicarboxylate), BDC (benzene dicarboxylate), ATC
(adamantane tetracarboxylate), BTC (benzene tricarboxylate), BTB
(benzene tribenzoate), MTB (methane tetrabenzoate) and ATB
(adamantane tribenzoate).
Besides the at least bidentate organic compound, the framework
material as used in accordance with the present invention may also
comprise one or more monodentate ligand(s), which is/are preferably
selected from the following monodentate substances and/or
derivatives thereof: a. alkyl amines and their corresponding alkyl
ammonium salts, containing linear, branched, or cyclic aliphatic
groups, having from 1 to 20 carbon atoms (and their corresponding
ammonium salts); b. aryl amines and their corresponding aryl
ammonium salts having from 1 to 5 phenyl rings; c. alkyl
phosphonium salts, containing linear, branched, or cyclic aliphatic
groups, having from 1 to 20 carbon atoms; d. aryl phosphonium
salts, having from 1 to 5 phenyl rings; e. alkyl organic acids and
the corresponding alkyl organic anions (and salts) containing
linear, branched, or cyclic aliphatic groups, having from 1 to 20
carbon atoms; f. aryl organic acids and their corresponding aryl
organic anions and salts, having from 1 to 5 phenyl rings; g.
aliphatic alcohols, containing linear, branched, or cyclic
aliphatic groups, having from 1 to 20 carbon atoms; h. aryl
alcohols having from 1 to 5 phenyl rings; i. inorganic anions from
the group consisting of: sulfate, nitrate, nitrite, sulfite,
bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate,
diphosphate, triphosphate, phosphite, chloride, chlorate, bromide,
bromate, iodide, iodate, carbonate, bicarbonate, and the
corresponding acids and salts of the aforementioned inorganic
anions, J. ammonia, carbon dioxide, methane, oxygen, ethylene,
hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene,
naphthalene, thiophene, pyridine, acetone, 1-2-dichloroethane,
methylenechloride, tetrahydrofuran, ethanolamine, triethylamine and
trifluoromethylsulfonic acid.
Further details regarding the at least bidentate organic compounds
and the monodentate substances, from which the ligands of the
framework material as used in the present application are derived,
can be taken from EP-A 0 790 253, whose respective content is
incorporated into the present application by reference.
Within the present application, framework materials of the kind
described herein, which comprise Zn.sup.2+ as a metal ion and
ligands derived from terephthalic acid as the bidentate compound,
are particularly preferred. Said framework materials are known as
MOF-5 in the literature.
Further metal ions, at least bidentate organic compounds and
mono-dentate substances, which are respectively useful for the
preparation of the framework materials used in the present
invention as well as processes for their preparation are
particularly disclosed in EP-A 0 790 253, U.S. Pat. No. 5,648,508
and DE 10111230.0.
As solvents, which are particularly useful for the preparation of
MOF-5, in addition to the solvents disclosed in the
above-referenced literature, dimethyl formamide, diethyl formamide
and N-methylpyrollidone, alone, in combination with each other or
in combination with other solvents may be used. Within the
preparation of the framework materials, particularly within the
preparation of MOF-5, the solvents and mother liquors are recycled
after crystallization in order to save costs and materials.
The pore sizes of the metal-organic framework can be adjusted by
selecting suitable organic ligands and/or bidendate compounds
(=linkers). Generally, the larger the linker, the larger the pore
size. Any pore size that is still supported by a the metal-organic
framework in the absence of a host and at temperatures of at least
200.degree. C. is conceivable. Pore sizes ranging from 0.2 nm to 30
nm are preferred, with pore sizes ranging from 0.3 nm to 3 nm being
particularly preferred.
In the following, examples of metal-organic framework materials
(MOFs) are given to illustrate the general concept given above.
These specific examples, however, are not meant to limit the
generality and scope of the present application.
By way of example, a list of metal-organic framework materials
already synthesized and characterized is given below. This also
includes novel isoreticular metal organic framework materials
(IR-MOFs), which may be used in the framework of the present
application. Such materials having the same framework topology
while displaying different pore sizes and crystal densities are
described, for example in M. Eddouadi et al., Science 295 (2002)
469, which is incorporated into the present application by
reference.
The solvents used are of particular importance for the synthesis of
these materials and are therefore mentioned in the table. The
values for the cell parameters (angles .alpha., .beta. and .gamma.
as well as the spacings a, b and c, given in Angstrom) have been
obtained by x-ray diffraction and represent the space group given
in the table as well.
Ingredients molar ratios Space MOF-n M + L Solvents .alpha. .beta.
.gamma. a b c Group MOF-0 Zn(NO.sub.3).sub.2.6H.sub.2 O ethanol 90
90 120 16.711 16.711 14.189 P6(3)/Mcm H.sub.3 (BTC) MOF-2
Zn(NO.sub.3).sub.2.6H.sub.2 O DMF 90 102.8 90 6.718 15.49 12.43
P2(1)/n (0.246 mmol) toluene H.sub.2 (BDC) 0.241 mmol) MOF-3
Zn(NO.sub.3).sub.2.6H.sub.2 O DMF 99.72 111.11 108.4 9.726 9.911
10.45 P-1 (1.89 mmol) MeOH H.sub.2 (BDC) (1.93 mmol) MOF-4
Zn(NO.sub.3).sub.2.6H.sub.2 O ethanol 90 90 90 14.728 14.728 14.728
P2(1)3 (1.00 mmol) H.sub.3 (BTC) (0.5 mmol) MOF-5
Zn(NO.sub.3).sub.2.6H.sub.2 O DMF 90 90 90 25.669 25.669 25.669
Fm-3m (2.22 mmol) chloro- H.sub.2 (BDC) benzene (2.17 mmol) MOF-38
Zn(NO.sub.3).sub.2.6H.sub.2 O DMF 90 90 90 20.657 20.657 17.84 I4cm
(0.27 mmol) chloro- H.sub.3 (BTC) benzene (0.15 mmol) MOF-31
Zn(NO.sub.3).sub.2.6H.sub.2 O ethanol 90 90 90 10.821 10.821 10.821
Pn(-3)m Zn(ADC).sub.2 0.4 mmol H.sub.2 (ADC) 0.8 mmol MOF-12
Zn(NO.sub.3).sub.2.6H.sub.2 O ethanol 90 90 90 15.745 16.907 18.167
Pbca Zn.sub.2 (ATC) 0.3 mmol H.sub.4 (ATC) 0.15 mmol MOF-20
Zn(NO.sub.3).sub.2.6H.sub.2 O DMF 90 92.13 90 8.13 16.444 12.807
P2(1)/c ZnNDC 0.37 mmol chloro- H.sub.2 NDC benzene 0.36 mmol
MOF-37 Zn(NO.sub.3).sub.2.6H.sub.2 O DEF 72.38 83.16 84.33 9.952
11.576 15.556 P-1 0.2 mmol chloro- H.sub.2 NDC benzene 0.2 mmol
MOF-8 Tb(NO.sub.3).sub.3.5H.sub.2 O DMSO 90 115.7 90 19.83 9.822
19.183 C2/c Tb.sub.2 (ADC) 0.10 mmol MeOH H.sub.2 ADC 0.20 mmol
MOF-9 Tb(NO.sub.3).sub.3.5H.sub.2 O DMSO 90 102.09 90 27.056 16.795
28.139 C2/c Tb.sub.2 (ADC) 0.08 mmol H.sub.2 ADB 0.12 mmol MOF-6
Tb(NO.sub.3).sub.3.5H.sub.2 O DMF 90 91.28 90 17.599 19.996 10.545
P21/c 0.30 mmol MeOH H.sub.2 (BDC) 0.30 mmol MOF-7
Tb(NO.sub.3).sub.3.5H.sub.2 O H.sub.2 O 102.3 91.12 101.5 6.142
10.069 10.096 P-1 0.15 mmol H.sub.2 (BDC) 0.15 mmol MOF-69A
Zn(NO.sub.3).sub.2.6H.sub.2 O DEF 90 111.6 90 23.12 20.92 12 C2/c
0.083 mmol H.sub.2 O.sub.2 4,4'BPDC MeNH.sub.2 0.041 mmol MOF-69B
Zn(NO.sub.3).sub.2.6H.sub.2 O DEF 90 95.3 90 20.17 18.55 12.16 C2/c
0.083 mmol H.sub.2 O.sub.2 2,6-NCD MeNH.sub.2 0.041 mmol MOF-11
Cu(NO.sub.3).sub.2 2.5H.sub.2 O H.sub.2 O 90 93.86 90 12.987 11.22
11.336 C2/c Cu.sub.2 (ATC) 0.47 mmol H.sub.2 ATC 0.22 mmol MOF-11
90 90 90 8.4671 8.4671 14.44 P42/mmc Cu.sub.2 (ATC) dehydr. MOF-14
Cu(NO.sub.3).sub.2 2.5H.sub.2 O H.sub.2 O 90 90 90 26.946 26.946
26.946 Im-3 Cu.sub.3 (BTB) 0.28 mmol DMF H.sub.3 BTB EtOH 0.052
mmol MOF-32 Cd(NO.sub.3).sub.2.4H.sub.2 O H.sub.2 O 90 90 90 13.468
13.468 13.468 P(-4)3m Cd(ATC) 0.24 mmol NaOH H.sub.4 ATC 0.10 mmol
MOF-33 ZnCl.sub.2 H.sub.2 O 90 90 90 19.561 15.255 23.404 Imma
Zn.sub.2 (ATB) 0.15 mmol DMF H.sub.4 ATB EtOH 0.02 mmol MOF-34
Ni(NO.sub.3).sub.2.6H.sub.2 O H.sub.2 O 90 90 90 10.066 11.163
19.201 P2.sub.1 2.sub.1 2.sub.1 Ni(ATC) 0.24 mmol NaOH H.sub.4 ATC
0.10 mmol MOF-36 Zn(NO.sub.3).sub.2.4H.sub.2 O H.sub.2 O 90 90 90
15.745 16.907 18.167 Pbca Zn.sub.2 (MTB) 0.20 mmol DMF H.sub.4 MTB
0.04 mmol MOF-39 Zn(NO.sub.3).sub.2 4H.sub.2 O H.sub.2 O 90 90 90
17.158 21.591 25.308 Pnma Zn.sub.3 O(HBTB) 0.27 mmol DMF H.sub.3
BTB EtOH 0.07 mmol NO305 FeCl.sub.2.4H.sub.2 O DMF 90 90 120 8.2692
8.2692 63.566 R-3c 5.03 mmol formic acid 86.90 mmol NO306A
FeCl.sub.2.4H.sub.2 O DEF 90 90 90 9.9364 18.374 18.374 Pbcn 5.03
mmol formic acid 86.90 mmol NO29 Mn(Ac).sub.2.4H.sub.2 O DMF 120 90
90 14.16 33.521 33.521 P-1 MOF-0 like 0.46 mmol H.sub.3 BTC 0.69
mmol BPR48 Zn(NO.sub.3).sub.2 6H.sub.2 O DMSO 90 90 90 14.5 17.04
18.02 Pbca A2 0.012 mmol toluene H.sub.2 BDC 0.012 mmol BPR69
Cd(NO.sub.3).sub.2 4H.sub.2 O DMSO 90 98.76 90 14.16 15.72 17.66 Cc
B1 0.0212 mmol H.sub.2 BDC 0.0428 mmol BPR92
Co(NO.sub.3).sub.2.6H.sub.2 O NMP 106.3 107.63 107.2 7.5308 10.942
11.025 P1 A2 0.018 mmol H.sub.2 BDC 0.018 mmol BPR95
Cd(NO.sub.3).sub.2 4H.sub.2 O NMP 90 112.8 90 14.460 11.085 15.829
P2(1)/n C5 0.012 mmol H.sub.2 BDC 0.36 mmol Cu C.sub.6 H.sub.4
O.sub.6 Cu(NO.sub.3).sub.2.2.5H.sub.2 O DMF 90 105.29 90 15.259
14.816 14.13 P2(1)/c 0.370 mmol chloro- H.sub.2 BDC(OH).sub.2
benzene 0.37 mmol M(BTC) Co(SO.sub.4) H.sub.2 O DMF Same as MOF-0
MOF-0 like 0.055 mmol H.sub.3 BTC 0.037 mmol Tb(C.sub.6 H.sub.4
O.sub.6) Tb(NO.sub.3).sub.3.5H.sub.2 O DMF 104.6 107.9 97.147
10.491 10.981 12.541 P-1 0.370 mmol chloro- H.sub.2 (C.sub.6
H.sub.4 O.sub.6) benzene 0.56 mmol Zn(C.sub.2 O.sub.4) ZnCl.sub.2
DMF 90 120 90 9.4168 9.4168 8.464 P(-3)1m 0.370 mmol chloro- oxalic
acid benzene 0.37 mmol Co(CHO) Co(NO.sub.3).sub.2.5H.sub.2 O DMF 90
91.32 90 11.328 10.049 14.854 P2(1)/n 0.043 mmol formic acid 1.60
mmol Cd(CHO) Cd(NO.sub.3).sub.2.4H.sub.2 O DMF 90 120 90 8.5168
8.5168 22.674 R-3c 0.185 mmol formic acid 0.185 mmol Cu(C.sub.3
H.sub.2 O.sub.4) Cu(NO.sub.3).sub.2.2.5H.sub.2 O DMF 90 90 90 8.366
8.366 11.919 P43 0.043 mmol malonic acid 0.192 mmol Zn.sub.6
(NDC).sub.5 Zn(NO.sub.3).sub.2.6H.sub.2 O DMF 90 95.902 90 19.504
16.482 14.64 C2/m MOF-48 0.097 mmol chloro- 14 NDC benzene 0.069
mmol H.sub.2 O.sub.2 MOF-47 Zn(NO.sub.3).sub.2 6H.sub.2 O DMF 90
92.55 90 11.303 16.029 17.535 P2(1)/c 0.185 mmol chloro- H.sub.2
(BDC[CH.sub.3 ].sub.4) benzene 0.185 mmol H.sub.2 O.sub.2 MO25
Cu(NO.sub.3).sub.2.2.5H.sub.2 O DMF 90 112.0 90 23.880 16.834
18.389 P2(1)/c 0.084 mmol BPhDC 0.085 mmol Cu-Thio
Cu(NO.sub.3).sub.2.2.5H.sub.2 O DEF 90 113.6 90 15.4747 14.514
14.032 P2(1)/c 0.084 mmol thiophene dicarboxylic 0.085 mmol ClBDC1
Cu(NO.sub.3).sub.2.2.5H.sub.2 O0.0 DMF 90 105.6 90 14.911 15.622
18.413 C2/c 84 mmol H.sub.2 (BDCCl.sub.2) 0.085 mmol MOF-101
Cu(NO.sub.3).sub.2.2.5H.sub.2 O DMF 90 90 90 21.607 20.607 20.073
Fm3m 0.084 mmol BrBDC 0.085 mmol Zn.sub.3 (BTC).sub.2 ZnCl.sub.2
DMF 90 90 90 26.572 26.572 26.572 Fm-3m 0.033 mmol EtOH H.sub.3 BTC
base 0.033 mmol added MOF-j Co(CH.sub.3 CO.sub.2).sub.2.4H.sub.2 O
H.sub.2 O 90 112.0 90 17.482 12.963 6.559 C2 (1.65 mmol) H.sub.3
(BZC) (0.95 mmol) MOF-n Zn(NO.sub.3).sub.2.6H.sub.2 O ethanol 90 90
120 16.711 16.711 14.189 P6(3)/mcm H.sub.3 (BTC) PbBDC
Pb(NO.sub.3).sub.2 DMF 90 102.7 90 8.3639 17.991 9.9617 P2(1)/n
(0.181 mmol) ethanol H.sub.2 (BDC) (0.181 mmol) Znhex
Zn(NO.sub.3).sub.2.6H.sub.2 O DMF 90 90 120 37.1165 37.117 30.019
P3(1)c (0.171 mmol) p-xylene H.sub.3 BTB ethanol (0.114 mmol) AS16
FeBr.sub.2 DMF 90 90.13 90 7.2595 8.7894 19.484 P2(1)c 0.927 mmol
anhydr. H.sub.2 (BDC) 0.927 mmol
AS27-2 FeBr.sub.2 DMF 90 90 90 26.735 26.735 26.735 Fm3m 0.927 mmol
anhydr. H.sub.3 (BDC) 0.464 mmol AS32 FeCl.sub.3 DMF 90 90 120
12.535 12.535 18.479 P6(2)c 1.23 mmol anhydr. H.sub.2 (BDC) ethanol
1.23 mmol AS54-3 FeBr.sub.2 DMF 90 109.98 90 12.019 15.286 14.399
C2 0.927 anhydr. BPDC n-propanol 0.927 mmol AS61-4 FeBr.sub.2
pyridine 90 90 120 13.017 13.017 14.896 P6(2)c 0.927 mmol anhydr.
m-BDC 0.927 mmol AS68-7 FeBr.sub.2 DMF 90 90 90 18.3407 10.036
18.039 Pca2.sub.1 0.927 mmol anhydr. m-BDC Pyridine 1.204 mmol
Zn(ADC) Zn(NO.sub.3).sub.2.6H.sub.2 O DMF 90 99.85 90 16.764 9.349
9.635 C2/c 0.37 mmol chloro- H.sub.2 (ADC) benzene 0.36 mmol MOF-12
Zn(NO.sub.3).sub.2.6H.sub.2 O ethanol 90 90 90 15.745 16.907 18.167
Pbca Zn.sub.2 (ATC) 0.30 mmol H.sub.4 (ATC) 0.15 mmol MOF-20
Zn(NO.sub.3).sub.2.6H.sub.2 O DMF 90 92.13 90 8.13 16.444 12.807
P2(1)/c ZnNDC 0.37 mmol chloro- H.sub.2 NDC benzene 0.36 mmol
MOF-37 Zn(NO.sub.3).sub.2.6H.sub.2 O DEF 72.38 83.16 84.33 9.952
11.576 15.556 P-1 0.20 mmol chloro- H.sub.2 NDC benzene 0.20 mmol
Zn(NDC) Zn(NO.sub.3).sub.2.6H.sub.2 O DMSO 68.08 75.33 88.31 8.631
10.207 13.114 P-1 (DMSO) H.sub.2 NDC Zn(NDC)
Zn(NO.sub.3).sub.2.6H.sub.2 O 90 99.2 90 19.289 17.628 15.052 C2/c
H.sub.2 NDC Zn(HPDC) Zn(NO.sub.3).sub.2.4H.sub.2 O DMF 107.9 105.06
94.4 8.326 12.085 13.767 P-1 0.23 mmol H.sub.2 O H.sub.2 (HPDC)
0.05 mmol Co(HPDC) Co(NO.sub.3).sub.2.6H.sub.2 O DMF 90 97.69 90
29.677 9.63 7.981 C2/c 0.21 mmol H.sub.2 O/ H.sub.2 (HPDC) ethanol
0.06 mmol Zn.sub.3 (PDC)2.5 Zn(NO.sub.3).sub.2.4H.sub.2 O DMF/
79.34 80.8 85.83 8.564 14.046 26.428 P-1 0.17 mmol CIBz H.sub.2
(HPDC) H.sub.2 O/ 0.05 mmol TEA Cd.sub.2 (TPDC)2
Cd(NO.sub.3).sub.2.4H.sub.2 O methanol/ 70.59 72.75 87.14 10.102
14.412 14.964 P-1 0.06 mmol CHP H.sub.2 (HPDC) H.sub.2 O 0.06 mmol
Tb(PDC)1.5 Tb(NO.sub.3).sub.3.5H.sub.2 O DMF 109.8 103.61 100.14
9.829 12.11 14.628 P-1 0.21 mmol H.sub.2 O/ H.sub.2 (PDC) ethanol
0.034 mmol ZnDBP Zn(NO.sub.3).sub.2.6H.sub.2 O MeOH 90 93.67 90
9.254 10.762 27.93 P2/n 0.05 mmol dibenzylphosphate 0.10 mmol
Zn.sub.3 (BPDC) ZnBr.sub.2 DMF 90 102.76 90 11.49 14.79 19.18 P21/n
0.021 mmol 4,4'BPDC 0.005 mmol CdBDC Cd(NO.sub.3).sub.2.4H.sub.2 O
DMF 90 95.85 90 11.2 11.11 16.71 P21/n 0.100 mmol Na.sub.2
SiO.sub.3 H.sub.2 (BDC) (aq) 0.401 mmol Cd-mBDC
Cd(NO.sub.3).sub.2.4H.sub.2 O DMF 90 101.1 90 13.69 18.25 14.91
C2/c 0.009 mmol MeNH.sub.2 H.sub.2 (mBDC) 0.018 mmol Zn.sub.4 OBNDC
Zn(NO.sub.3).sub.2.6H.sub.2 O DEF 90 90 90 22.35 26.05 59.56 Fmmm
0.041 mmol MeNH.sub.2 BNDC H.sub.2 O.sub.2 Eu(TCA)
Eu(NO.sub.3).sub.3.6H.sub.2 O DMF 90 90 90 23.325 23.325 23.325
Pm-3n 0.14 mmol chloro- TCA benzene 0.026 mmol Tb(TCA)
Tb(NO.sub.3).sub.3.6H.sub.2 O DMF 90 90 90 23.272 23.272 23.372
Pm-3n 0.069 mmol chloro- TCA benzene 0.026 mmol Formate
Ce(NO.sub.3).sub.3.6H.sub.2 O H.sub.2 O 90 90 120 10.668 10.667
4.107 R-3m 0.138 mmol ethanol Formaic acid 0.43 mmol
FeCl.sub.2.4H.sub.2 O DMF 90 90 120 8.2692 8.2692 63.566 R-3c 5.03
mmol Formic acid 86.90 mmol FeCl.sub.2.4H.sub.2 O DEF 90 90 90
9.9364 18.374 18.374 Pbcn 5.03 mmol Formic acid 86.90 mmol
FeCl.sub.2.4H.sub.2 O DEF 90 90 90 8.335 8.335 13.34 P-31c 5.03
mmol Formic acid 86.90 mmol NO330 FeCl.sub.2.4H.sub.2 O formamide
90 90 90 8.7749 11.655 8.3297 Pnna 0.50 mmol Formic acid 8.69 mmol
NO332 FeCl.sub.2.4H.sub.2 O DIP 90 90 90 10.0313 18.808 18.355 Pbcn
0.50 mmol Formic acid 8.69 mmol NO333 FeCl.sub.2.4H.sub.2 O DBF 90
90 90 45.2754 23.861 12.441 Cmcm 0.50 mmol Formic acid 8.69 mmol
NO335 FeCl.sub.2.4H.sub.2 O CHF 90 91.372 90 11.5964 10.187 14.945
P21/n 0.50 mmol Formic acid 8.69 mmol NO336 FeCl.sub.2.4H.sub.2 O
MFA 90 90 90 11.7945 48.843 8.4136 Pbcm 0.50 mmol Formic acid 8.69
mmol NO13 Mn(Ac).sub.2.4H.sub.2O ethanol 90 90 90 18.66 11.762
9.418 Pbcn 0.46 mmol Bezoic acid 0.92 mmol Bipyridine 0.46 mmol
NO29 Mn(Ac).sub.2.4H.sub.2 O DMF 120 90 90 14.16 33.521 33.521 P-1
MOF-0 0.46 mmol Like H.sub.3 BTC 0.69 mmol Mn(hfac).sub.2
Mn(Ac).sub.2.4H.sub.2 O ether 90 95.32 90 9.572 17.162 14.041 C2/c
(O.sub.2 CC.sub.6 H.sub.5) 0.46 mmol Hfac 0.92 mmol Bipyridine 0.46
mmol BPR43G2 Zn(NO.sub.3).sub.2.6H.sub.2 O DMF 90 91.37 90 17.96
6.38 7.19 C2/c 0.0288 mmol CH.sub.3 CN H.sub.2 BDC 0.0072 mmol
BPR48A2 Zn(NO.sub.3).sub.2 6H.sub.2 O DMSO 90 90 90 14.5 17.04
18.02 Pbca 0.012 mmol toluene H.sub.2 BDC 0.012 mmol BPR49B1
Zn(NO.sub.3).sub.2 6H.sub.2 O DMSO 90 91.172 90 33.181 9.824 17.884
C2/c 0.024 mmol methanol H.sub.2 BDC 0.048 mmol BPR56E1
Zn(NO.sub.3).sub.2 6H.sub.2 O DMSO 90 90.096 90 14.5873 14.153
17.183 P2(1)/n 0.012 mmol n-propanol H.sub.2 BDC 0.024 mmol
BPR68D10 Zn(NO.sub.3).sub.2 6H.sub.2 O DMSO 90 95.316 90 10.0627
10.17 16.413 P2(1)/c 0.0016 mmol benzene H.sub.3 BTC 0.0064 mmol
BPR69B1 Cd(NO.sub.3).sub.2 4H.sub.2 O DMSO 90 98.76 90 14.16 15.72
17.66 Cc 0.0212 mmol H.sub.2 BDC 0.0428 mmol BPR73E4
Cd(NO.sub.3).sub.2 4H.sub.2 O DMSO 90 92.324 90 8.7231 7.0568
18.438 P2(1)/n 0.006 mmol toluene H.sub.2 BDC 0.003 mmol BPR76D5
Zn(NO.sub.3).sub.2 6H.sub.2 O DMSO 90 104.17 90 14.4191 6.2599
7.0611 Pc 0.0009 mmol H.sub.2 BzPDC 0.0036 mmol BPR80B5
Cd(NO.sub.3).sub.2.4H.sub.2 O DMF 90 115.11 90 28.049 9.184 17.837
C2/c 0.018 mmol H.sub.2 BDC 0.036 mmol BPR80H5 Cd(NO.sub.3).sub.2
4H.sub.2 O DMF 90 119.06 90 11.4746 6.2151 17.268 P2/c 0.027 mmol
H.sub.2 BDC 0.027 mmol BPR82C6 Cd(NO.sub.3).sub.2 4H.sub.2 O DMF 90
90 90 9.7721 21.142 27.77 Fdd2 0.0068 mmol H.sub.2 BDC 0.202 mmol
BPR86C3 Co(NO.sub.3).sub.2 6H.sub.2 O DMF 90 90 90 18.3449 10.031
17.983 Pca2(1) 0.0025 mmol H.sub.2 BDC 0.075 mmol BPR86H6
Cd(NO.sub.3).sub.2.6H.sub.2 O DMF 80.98 89.69 83.412 9.8752 10.263
15.362 P-1 0.010 mmol H.sub.2 BDC 0.010 mmol Co(NO.sub.3).sub.2
6H.sub.2 O NMP 106.3 107.63 107.2 7.5308 10.942 11.025 P1 BPR95A2
Zn(NO.sub.3).sub.2 6H.sub.2 O NMP 90 102.9 90 7.4502 13.767 12.713
P2(1)/c 0.012 mmol H.sub.2 BDC 0.012 mmol CuC.sub.6 F.sub.4 O.sub.4
Cu(NO.sub.3).sub.2.2.5H.sub.2 O DMF 90 98.834 90 10.9675 24.43
22.553 P2(1)/n 0.370 mmol chloro- H.sub.2 BDC(OH).sub.2 benzene
0.37 mmol
Fe Formic FeCl.sub.2.4H.sub.2 O DMF 90 91.543 90 11.495 9.963 14.48
P2(1)/n 0.370 mmol Formic acid 0.37 mmol Mg Formic
Mg(NO.sub.3).sub.2.6H.sub.2 O DMF 90 91.359 90 11.383 9.932 14.656
P2(1)/n 0.370 mmol Formic acid 0.37 mmol MgC.sub.6 H.sub.4 O.sub.6
Mg(NO.sub.3).sub.2.6H.sub.2 O DMF 90 96.624 90 17.245 9.943 9.273
C2/c 0.370 mmol H.sub.2 BDC(OH).sub.2 0.37 mmol Zn C.sub.2 H.sub.4
BDC ZnCl.sub.2 DMF 90 94.714 90 7.3386 16.834 12.52 P2(1)/n MOF-38
0.44 mmol CBBDC 0.261 mmol MOF-49 ZnCl.sub.2 DMF 90 93.459 90
13.509 11.984 27.039 P2/c 0.44 mmol CH3CN m-BDC 0.261 mmol MOF-26
Cu(NO.sub.3).sub.2.5H.sub.2 O DMF 90 95.607 90 20.8797 16.017
26.176 P2(1)/n 0.084 mmol DCPE 0.085 mmol MOF-112
Cu(NO.sub.3).sub.2.2.5H.sub.2 O DMF 90 107.49 90 29.3241 21.297
18.069 C2/c 0.084 mmol ethanol o-Br-m-BDC 0.085 mmol MOF-109
Cu(NO.sub.3).sub.2.2.5H.sub.2 O DMF 90 111.98 90 23.8801 16.834
18.389 P2(1)/c 0.084 mmol KDB 0.085 mmol MOF-111
Cu(NO.sub.3).sub.2.2.5H.sub.2 O DMF 90 102.16 90 10.6767 18.781
21.052 C2/c 0.084 mmol ethanol o-BrBDC 0.085 mmol MOF-110
Cu(NO.sub.3).sub.2.2.5H.sub.2 O DMF 90 90 120 20.0652 20.065 20.747
R-3/m 0.084 mmol thiophene dicarboxylic 0.085 mmol MOF-107
Cu(NO.sub.3).sub.2.2.5H.sub.2 O DEF 104.8 97.075 95.206 11.032
18.067 18.452 P-1 0.084 mmol thiophene dicarboxylic 0.085 mmol
MOF-108 Cu(NO.sub.3).sub.2.2.5H.sub.2 O DBF/ 90 113.63 90 15.4747
14.514 14.032 C2/c 0.084 mmol methanol thiophene dicarboxylic 0.085
mmol MOF-102 Cu(NO.sub.3).sub.2.2.5H.sub.2 O DMF 91.63 106.24
112.01 9.3845 10.794 10.831 P-1 0.084 mmol H.sub.2 (BDCCl.sub.2)
0.085 mmol Clbdc1 Cu(NO.sub.3).sub.2.2.5H.sub.2 O DEF 90 105.56 90
14.911 15.622 18.413 P-1 0.084 mmol H.sub.2 (BDCCl.sub.2) 0.085
mmol Cu(NMOP) Cu(NO.sub.3).sub.2.2.5H.sub.2 O DMF 90 102.37 90
14.9238 18.727 15.529 P2(1)/m 0.084 mmol NBDC 0.085 mmol Tb(BTC)
Tb(NO.sub.3).sub.3.5H.sub.2 O DMF 90 106.02 90 18.6986 11.368
19.721 0.033 mmol H.sub.3 BTC 0.033 mmol Zn.sub.3 (BTC).sub.2
ZnCl.sub.2 DMF 90 90 90 26.572 26.572 26.572 Fm-3m Honk 0.033 mmol
ethanol H.sub.3 BTC 0.033 mmol Zn.sub.4 O(NDC)
Zn(NO.sub.3).sub.2.4H.sub.2 O DMF 90 90 90 41.5594 18.818 17.574
aba2 0.066 mmol ethanol 14NDC 0.066 mmol CdTDC
Cd(NO.sub.3).sub.2.4H.sub.2 O DMF 90 90 90 12.173 10.485 7.33 Pmma
0.014 mmol H.sub.2 O thiophene 0.040 mmol DABCO 0.020 mmol IRMOF-2
Zn(NO.sub.3).sub.2.4H.sub.2 O DEF 90 90 90 25.772 25.772 25.772
Fm-3m 0.160 mmol o-Br-BDC 0.60 mmol IRMOF-3
Zn(NO.sub.3).sub.2.4H.sub.2 O DEF 90 90 90 25.747 25.747 25.747
Fm-3m 0.20 mmol ethanol H.sub.2 N-BDC 0.60 mmol IRMOF-4
Zn(NO.sub.3).sub.2.4H.sub.2 O DEF 90 90 90 25.849 25.849 25.849
Fm-3m 0.11 mmol [C.sub.3 H.sub.7 O].sub.2 -BDC 0.48 mmol IRMOF-5
Zn(NO.sub.3).sub.2.4H.sub.2 O DEF 90 90 90 12.882 12.882 12.882
Pm-3m 0.13 mmol [C.sub.5 H.sub.11 O].sub.2 -BDC 0.50 mmol IRMOF-6
Zn(NO.sub.3).sub.2.4H.sub.2 O DEF 90 90 90 25.842 25.842 25.842
Fm-3m 0.20 mmol [C.sub.2 H.sub.4 ]-BDC 0.60 mmol IRMOF-7
Zn(NO.sub.3).sub.2.4H.sub.2 O DEF 90 90 90 12.914 12.914 12.914
Pm-3m 0.07 mmol 1,4NDC 0.20 mmol IRMOF-8
Zn(NO.sub.3).sub.2.4H.sub.2 O DEF 90 90 90 30.092 30.092 30.092
Fm-3m 0.55 mmol 2,6NDC 0.42 mmol IRMOF-9
Zn(NO.sub.3).sub.2.4H.sub.2 O DEF 90 90 90 17.147 23.322 25.255
Pnnm 0.05 mmol BPDC 0.42 mmol IRMOF-10 Zn(NO.sub.3).sub.2.4H.sub.2
O DEF 90 90 90 34.281 34.281 34.281 Fm-3m 0.02 mmol BPDC 0.012 mmol
IRMOF-11 Zn(NO.sub.3).sub.2.4H.sub.2 O DEF 90 90 90 24.822 24.822
56.734 R-3m 0.05 mmol HPDC 0.20 mmol IRMOF-12
Zn(NO.sub.3).sub.2.4H.sub.2 O DEF 90 90 90 34.281 34.281 34.281
Fm-3m 0.017 mmol HPDC 0.12 mmol IRMOF-13
Zn(NO.sub.3).sub.2.4H.sub.2 O DEF 90 90 90 24.822 24.822 56.734
R-3m 0.048 mmol PDC 0.31 mmol IRMOF-14 Zn(NO.sub.3).sub.2.4H.sub.2
O DEF 90 90 90 34.381 34.381 34.381 Fm-3m 0.17 mmol PDC 0.12 mmol
IRMOF-15 Zn(NO.sub.3).sub.2.4H.sub.2 O DEF 90 90 90 21.459 21.459
21.459 Im-3m 0.063 mmol TPDC 0.025 mmol IRMOF-16
Zn(NO.sub.3).sub.2.4H.sub.2 O DEF 90 90 90 21.49 21.49 21.49 Pm-3m
0.0126 mmol NMP TPDC 0.05 mmol ADC Acetylene dicarboxylic acid NDC
Naphtalene dicarboxylic acid BDC Benzene dicarboxylic acid ATC
Adamantane tetracarboxylic acid BTC Benzene tricarboxylic acid BTB
Benzene tribenzoate MTB Methane tetrabenzoate ATB Adamantane
tetrabenzoate ADB Adamantane dibenzoate
Examples for the synthesis of these materials as such can, for
example, be found in: J. Am. Chem. Soc. 123 (2001) pages 8241 seq.
or in Acc. Chem. Res. 31 (1998) pages 474 seq., which are fully
encompassed within the content of the present application with
respect to their respective content.
The separation of the framework materials, particularly of MOF-5,
from the mother liquor of the crystallization may be achieved by
procedures known in the art such as solid-liquid separations,
centrifugation, extraction, filtration, membrane filtration,
cross-flow filtration, flocculation using flocculation adjuvants
(non-ionic, cationic and anionic adjuvants) or by the addition of
pH shifting additives such as salts, acids or bases, by flotation,
as well as by evaporation of the mother liquor at elevated
temperature and/or in vacuo and concentrating of the solid. The
material obtained in this step is typically a fine powder and
cannot be used for most practical applications, e.g., in catalysis,
where shaped bodies are required.
In the context of the present invention, the term "shaped body"
refers to any solid body that has at least a two-dimensional outer
contour and extends to at least 0.02 mm in at least one direction
in space. No other restrictions apply, i.e., the body may take any
conceivable shape and may extend in any direction by any length so
long as it extends to at least 0.02 mm in one direction. In a
preferred embodiment, the shaped bodies do not extend to more than
50 mm and not to less than 0.02 mm in all directions. In a further
preferred embodiment, this range is limited from 1.5 mm to 5
mm.
As far as the geometry of these shaped bodies is concerned,
spherical or cylindrical bodies are preferred, as well as
disk-shaped pellets or any other suitable geometry. such as
honeycombs, meshes, hollow bodies, wire arrangements etc.
To form shaped bodies containing an active material, for example a
catalytically active material, several routes exist. Among them (i)
molding the active material alone or the active material in
combination with a binder and/or other components into a shaped
body, for example by pelletizing; (ii) applying the active material
onto a (porous) substrate, and (iii) supporting an active material
on a porous or non-porous substrate which is then molded into a
shaped body
are to be mentioned.
Although not limited with regard to the route to obtain shaped
bodies comprising metal-organic frameworks according to the present
invention, the above-recited routes are preferred within the
invention disclosed herein. Presently, zeolites are the most
commonly used porous active materials that are either molded into
shaped bodies or applied onto a (porous) support.
For the step of preparing shaped bodies containing at least one
metal-organic framework material, all processes of molding a powder
and/or crystallites together that are known to the expert are
conceivable. Also, all processes of applying an active component,
such as the metal-organic framework material, onto a substrate are
conceivable. Preparing shaped bodies by a process involving molding
is described first, followed by a description of the process of
applying said material onto a (porous) substrate.
In the context of the present invention, the term "molding" refers
to any process known to the expert in the field by which a
substance that does not fulfill the above-mentioned requirement of
a shaped body, i.e. any powder, powdery substance, array of
crystallites etc., can be formed into a shaped body that is stable
under the conditions of its intended use.
While the step of molding at least one metal-organic framework
material into a shaped body is mandatory, the following steps are
optional according to the present invention: (I) the molding may be
preceded by a step of mixing, (II) the molding may be preceded by a
step of preparing a paste-like mass or a fluid containing the
metal-organic framework, for example by adding solvents, binders or
other additional substances, (III) the molding may be followed by a
step of finishing, in particular a step of drying.
The mandatory step of molding, shaping or forming may be achieved
by any method known to expert to achieve agglomeration of a powder,
a suspension or a paste-like mass. Such methods are described, for
example, in Ullmann's Enzylopadie der Technischen Chemie, 4.sup.th
Edition, Vol. 2, p. 313 et seq., 1972, whose respective content is
incorporated into the present application by reference.
In general, the following main pathways can be discerned: (i)
briquetting, i.e. mechanical pressing of the powdery material, with
or without binders and/or other additives, (ii) granulating
(pelletizing), i.e. compacting of moistened powdery materials by
subjecting it to rotating movements, and (iii) sintering, i.e.
subjecting the material to be compacted to a thermal treatment. The
latter is somewhat limited for the material according to the
invention due to the limited temperature stability of the organic
materials (see discussion below).
Specifically, the molding step according to the invention is
preferably performed by using at least one method selected from the
following group: briquetting by piston presses, briquetting by
roller pressing, binderless briquetting, briquetting with binders,
pelletizing, compounding, melting, extruding, co-extruding,
spinning, deposition, foaming, spray drying, coating, granulating,
in particular spray granulating or granulating according to any
process known within the processing of plastics or any combination
of at least two of the aforementioned methods.
The preferred processes of molding are those in which the molding
is affected by extrusion in conventional extruders, for example
such that result in extrudates having a diameter of, usually, from
about 1 to about 10 mm, in particular from about 1.5 to about 5 mm.
Such extrusion apparatuses are described, for example, in Ullmann's
Enzylopadie der Technischen Chemie, 4th Edition, Vol. 2, p. 295 et
seq., 1972. In addition to the use of an extruder, an extrusion
press is preferably also used for molding.
The molding can be performed at elevated pressure (ranging from
atmospheric pressure to several 100 bar), at elevated temperatures
(ranging from room temperature to 300.degree. C.) or in a
protective atmosphere (noble gases, nitrogen or mixtures thereof).
Any combinations of these conditions is possible as well.
The step of molding can be performed in the presence of binders
and/or other additional substances that stabilize the materials to
be agglomerated. As to the at least one optional binder, any
material known to expert to promote adhesion between the particles
to be molded together can be employed. A binder, an organic
viscosity-enhancing compound and/or a liquid for converting the
material into a paste can be added to the metal-organic framework
material, with the mixture being subsequently compacted in a mixing
or kneading apparatus or an extruder. The resulting plastic
material can then be molded, in particular using an extrusion press
or an extruder, and the resulting moldings can then be subjected to
the optional step (III) of finishing, for example drying.
A number of inorganic compounds can be used as binders. For
example, according to U.S. Pat. No. 5,430,000, titanium dioxide or
hydrated titanium dioxide is used as the binder. Examples of
further prior art binders are: hydrated alumina or other
aluminum-containing binders (WO 94/29408); mixtures of silicon and
aluminum compounds (WO 94/13584); silicon compounds (EP-A 0 592
050); clay minerals (JP-A 03 037 156); alkoxysilanes (EP-B 0 102
544); amphiphilic substances; graphite.
Other conceivable binders are in principle all compounds used to
date for the purpose of achieving adhesion in powdery materials.
Compounds, in particular oxides, of silicon, of aluminum, of boron,
of phosphorus, of zirconium and/or of titanium are preferably used.
Of particular interest as a binder is silica, where the SiO.sub.2
may be introduced into the shaping step as a silica sol or in the
form of tetraalkoxysilanes. Oxides of magnesium and of beryllium
and clays, for example montmorillonites, kaolins, bentonites,
halloysites, dickites, nacrites and anauxites, may furthermore be
used as binders. Tetraalkoxysilanes are particularly used as
binders in the present invention. Specific examples are
tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and
tetrabutoxysilane, the analogous tetraalkoxytitanium and
tetraalkoxyzirconium compounds and trimethoxy-, triethoxy-,
tripropoxy- and tributoxy-aluminum, tetramethoxysilane and
tetraethoxysilane being particularly preferred.
In addition, organic viscosity-enhancing substances and/or
hydrophilic polymers, e.g. cellulose or polyacrylates may be used.
The organic viscosity-enhancing substance used may likewise be any
substance suitable for this purpose. Those preferred are organic,
in particular hydrophilic polymers, e.g., cellulose, starch,
polyacrylates, polymethacrylates, polyvinyl alcohol,
polyvinylpyrrolidone, polyisobutene and polytetrahydrofuran. These
substances primarily promote the formation of a plastic material
during the kneading, molding and drying step by bridging the
primary particles and moreover ensuring the mechanical stability of
the molding during the molding and the optional drying process.
There are no restrictions at all with regard to the optional liquid
which may be used to create a paste-like substance, either for the
optional step (I) of mixing or for the mandatory step of molding.
In addition to water, alcohols may be used, provided that they are
water-miscible. Accordingly, both monoalcohols of 1 to 4 carbon
atoms and water-miscible polyhydric alcohols may be used. In
particular, methanol, ethanol, propanol, n-butanol, isobutanol,
tert-butanol and mixtures of two or more thereof are used.
Amines or amine-like compounds, for example tetraalkylammonium
compounds or aminoalcohols, and carbonate-containing substances,
such as calcium carbonate, may be used as further additives. Such
further additives are described in EP-A 0 389 041, EP-A 0 200 260
and WO 95/19222, which are incorporated fully by reference in the
context of the present application.
Most, if not all, of the additive substances mentioned above may be
removed from the shaped bodies by drying or heating, optionally in
a protective atmosphere or under vacuum. In order to keep the
metal-organic framework intact, the shaped bodies are preferably
not exposed to temperatures exceeding 300.degree. C. However,
studies show that heating/drying under the aforementioned mild
conditions, in particular drying in vacuo, preferably well below
300.degree. C. is sufficient to at least remove organic compounds
out of the pores of the metal-organic framework (see the references
given with respect to metal-organic frameworks above). Generally,
the conditions are adapted and chosen depending upon the additive
substances used.
The order of addition of the components (optional solvent, binder,
additives, material with a metal-organic framework) is not
critical. It is possible either to add first the binder, then, for
example, the metal-organic framework material and, if required, the
additive and finally the mixture containing at least one alcohol
and/or water or to interchange the order with respect to any of the
aforementioned components.
As far as the optional step (I) of mixing is concerned, for
example, of the material containing a metal-organic framework and a
binder and optionally further process materials (=additional
materials), all methods known to the expert in the fields of
materials processing and unit operations can be used. If the mixing
occurs in the liquid phase, stirring is preferred, if the mass to
be mixed is paste-like, kneading and/or extruding are preferred and
if the components to be mixed are all in a solid, powdery state,
mixing is preferred. The use of atomizers, sprayers, diffusers or
nebulizers is conceivable as well if the state of the components to
be used allows the use thereof. For paste-like and powder-like
materials the use of static mixers, planetary mixers, mixers with
rotating containers, pan mixers, pug mills, shearing-disk mixers,
centrifugal mixers, sand mills, trough kneaders, internal mixers,
internal mixers and continuous kneaders are preferred. It is
explicitly included that a process of mixing may be sufficient to
achieve the molding, i.e., that the steps of mixing and molding
coincide.
The shaped body according to the invention is preferably
characterized by at least one of the following properties: (i) it
extends in at least one direction in space by at least 0.02 mm and
that it does not extend in any direction in space by more than 50
mm. (ii) it is pellet shaped and has a diameter in the range from
1.5 mm to 5 mm and a height in the range from 1 mm to 5 mm. (iii)
it has a resistance to pressure (crush strength) in the range from
2 N to 100 N.
As a second principal pathway for producing shaped bodies
containing at least one metal-organic framework material, applying
said material to a substrate is part of the present invention.
Preferably, the substrate is porous. In principle, all techniques
for contacting said material with said substrate are conceivable.
Specifically, all techniques used for contacting an active material
with a porous substrate known from the preparation of catalysts are
applicable.
The at least one method of contacting is selected from the group
comprising impregnating with a fluid, soaking in a fluid, spraying,
depositing from the liquid phase, depositing from gas phase (vapor
deposition), precipitating, co-precipitating, dipping-techniques,
coating.
As a porous substrate, each shaped body known to the expert can be
used, so long as the shaped body fulfills the general requirements
concerning its geometry as specified in the present application,
for example, in the points (i) to (iii) given above. Specifically,
the porous substrate that will be contacted with the metal-organic
framework material can be selected from the following group
containing alumina, activated alumina, hydrated alumina, silica
gels, silicates, diatomite, kaolin, magnesia, activated charcoal,
titanium dioxide, zeolites.
While porous substrates are the preferred embodiment, contacting of
the active material (metal-organic framework) with a nonporous body
and/or a two-dimensional substrate are conceivable as well. In the
case of applying a catalytically active material onto a non-porous
shaped body, shell catalysts are obtained. Such configurations, as
well as monolithic embodiments are explicitly included in the
present invention, so long as they contain at least one
metal-organic frame-work material.
Other embodiments customary in catalyst technologies such as
application of the active substance in a washcoat and/or
structuring the support in honeycombs or in channels or other
skeleton-shapes are preferred.
The shaped bodies according to the invention can be used in any
process known to the expert in which a porous body or a body with
channels or a porous body with channels provides an advantage over
solid bodies or powders. In particular, such applications include:
catalysts, support for catalysts, sorption, storage of fluids,
desiccants, ion exchanger materials, molecular sieves (separators),
materials for chromatography, materials for the selective release
and/or uptaking of molecules, molecular recognition, nanotubes,
nano-reactors.
In a preferred application, the shaped bodies according to the
invention are used as catalysts in fixed bed/packed bed reactors.
In principle, said shaped bodies can be used in gas phase reactions
or in liquid phase reactions, in which case the solid shaped bodies
are suspended in a slurry. In principle, the shaped bodies
according to the invention can be used to catalyze all reactions
known to the expert in which the presence of channels and/or pores
and/or active centers incorporated therein are known or believed to
increase the activity and/or selectivity and/or yield of said
reaction.
The invention is now further described by way of the following
examples, which are, however, not meant to limit the scope of the
present application.
EXAMPLE 1
Preparation of MOF-5
Molar Starting Material Amount Calculated Experimental terephthalic
acid 12.3 mmol 2.04 g 2.04 g zinc nitrate-tetra hy- 36.98 mmol 9.67
g 9.68 g drate diethylformamide 2568.8 mmol 282.2 g 282.2 g
(Merck)
The respective amounts of the starting materials given in the table
above were placed in a beaker in the order diethylformamide,
terephthalic acid and zinc nitrate. The resulting solution was
introduced into two autoclaves (250 ml), having inner walls which
were covered by teflon.
The crystallization occurred at 105.degree. C. and within twenty
hours. Subsequently, the orange solvent was decanted from the
yellow crystals, said crystals were again covered by 20 ml
dimethylformamide, the latter again being decanted. This procedure
was repeated three times. Subsequently, 20 ml chloroform were
poured onto the solid, which was washed and decanted by said
solvent two times.
The crystals (14.4 g), which were still moist, were introduced into
a vacuum device and first dried at room temperature in vacuo
(10.sup.-4 mbar). Afterwards, they were dried at 120.degree. C.
Subsequently, the resulting product was characterized by X-ray
powder diffraction and an adsorptive determination of micropores.
The determination of the sorption isotherm with argon (87K;
Micromeritics ASAP 2010) shows an isotherm of the type I, being
characteristic of microporous materials and having a specific
surface area of 3020 m.sup.2 /g, calculated according to Langmuir,
as well as a micropore volume of 0.97 ml/g (at a relative pressure
of p/p.sup.0 =0.4).
EXAMPLE 2
Preparing Pellets Containing MOF-5
Pressing of the pellets according to the invention was performed by
means of an eccentric press as provided by Korsch (Type EK0). Here,
the pellet-forming tool was chosen to be a matrix with a hole of a
diameter of 4.75 mm, thus leading to pellets of 4.75 mm diameter.
The mixture that was fed into the eccentric press consisted of
99.8% MOF-2 and 0.2% graphite, namely of 49.9 g MOF-5 powder and
0.1 g graphite. The two components have been mixed thoroughly in a
mixing flask. The procedure was performed under nitrogen
atmophere.
The adjustments of the eccentric press were as follows: (i) filling
height: 10 mm, (ii) penetrating depth of the upper stamp: 7 mm and
(iii) rounds per minute of the rotor: 20.
The shape of the pellet was as follows: (i) diameter: 4.75 mm and
(ii) height: 3 mm.
After the pellet-forming, the lateral pressure resistance to
pressure (crush strength) was measured with a hardness grading
device by Zwick to be 10 N/pellet with a standard deviation of 0.8
N/pellet.
* * * * *